112
S. Akine et al.
Kyritsakas, N.; Lehn, J.-M. Chem. Commun. 2003, 2868–
2869.
(100 MHz, CDCl3) d 56.15, 73.02, 73.62, 113.52, 116.38,
119.50, 120.47, 120.80, 121.32, 122.39, 122.87, 145.96,
147.01, 148.10, 150.33, 150.81, 152.00, 196.07. Anal.
calcd for C18H18N2O7z0.5EtOH: C, 57.43; H, 5.33; N, 7.05.
Found: C, 57.82; H, 5.04; N, 6.81.
(5) (a) Miyake, H.; Yoshida, K.; Sugimoto, H.; Tsukube, H.
J. Am. Chem. Soc. 2004, 126, 6524–6525. (b) Miyake, H.;
Sugimoto, H.; Tamiaki, H.; Tsukube, H. Chem. Commun.
2005, 4291–4293. (c) Miyake, H.; Kamon, H.; Miyahara, I.;
Sugimoto, H.; Tsukube, H. J. Am. Chem. Soc. 2008, 130,
792–793. (d) Miyake, H.; Hikita, M.; Itazaki, M.;
Nakazawa, H.; Sugimoto, H.; Tsukube, H. Chem. Eur. J.
2008, 14, 5393–5396.
4.5 Synthesis of ligand H8L4
A solution of diamine 3 (7.83 mg, 0.025 mmol) in ethanol
(1.5 mL) and chloroform (1 mL) was gradually added to a
solution of aldehyde 7 (18.7 mg, 0.050 mmol) in chloro-
form (1 mL) and ethanol (2 mL) at 55–608C. The mixture
was stirred at the same temperature for 3 h and cooled to
room temperature. The white precipitates were collected to
give H8L4 (12.7 mg, 0.0123 mmol, 50%) as colourless
crystals; m.p. 192–1948C; 1H NMR (400 MHz, CDCl3) d
3.91 (s, 6H), 4.49–4.53 (m, 16H), 6.77 (s, 6H), 6.81–6.93
(m, 6H), 8.230 (s, 2H), 8.235 (s, 2H), 8.238 (s, 2H), 8.26 (s,
2H), 9.63 (s, 2H), 9.65 (s, 2H), 9.66 (s, 2H), 9.73 (s, 2H).
Anal. calcd for C48H50N8O18zH2O: C, 55.17; H, 5.02; N,
10.72. Found: C, 55.22; H, 4.76; N, 11.04.
(6) For a review, see: Akine, S.; Nabeshima, T. Dalton Trans.
2009, 10395–10408.
(7) (a) Akine, S.; Taniguchi, T.; Nabeshima, T. Angew. Chem.,
Int. Ed. 2002, 41, 4670–4673. (b) Akine, S.; Taniguchi, T.;
Saiki, T.; Nabeshima, T. J. Am. Chem. Soc. 2005, 127, 540–
541. (c) Akine, S.; Matsumoto, T.; Taniguchi, T.;
Nabeshima, T. Inorg. Chem. 2005, 44, 3270–3274. (d)
Akine, S.; Taniguchi, T.; Nabeshima, T. Tetrahedron Lett.
2006, 47, 8419–8422. (e) Akine, S.; Taniguchi, T.;
Nabeshima, T. J. Am. Chem. Soc. 2006, 128, 15765–
15774. (f) Akine, S.; Kagiyama, S.; Nabeshima, T. Inorg.
Chem. 2007, 46, 9525–9527. (g) Akine, S.; Taniguchi, T.;
Nabeshima, T. Inorg. Chem. 2008, 47, 3255–3264. (h)
Akine, S.; Utsuno, F.; Nabeshima, T. IOP Conf. Ser.: Mater.
Sci. Eng. 2009, 1, 012009. (i) Akine, S.; Morita, Y.; Utsuno,
F.; Nabeshima, T. Inorg. Chem. 2009, 48, 10670–10678. (j)
Akine, S.; Kagiyama, S.; Nabeshima, T. Inorg. Chem. 2010,
49, 2141–2152. (k) Akine, S.; Akimoto, A.; Nabeshima, T.
Phosphorus, Sulfur Silicon Relat. Elem. 2010, 185, 1000–
1007.
4.6 Synthesis of ligand H10L5
A similar procedure starting with diamine 4 (13.4 mg,
0.025 mmol) and aldehyde 7 (18.7 mg, 0.050 mmol) gave
H10L5 (20.9 mg, 0.0167 mmol, 67%) as colourless crystals;
(8) (a) Akine, S.; Taniguchi, T.; Matsumoto, T.; Nabeshima, T.
Chem. Commun. 2006, 4961–4963. (b) Akine, S.;
Matsumoto, T.; Nabeshima, T. Chem. Commun. 2008,
4604–4606.
1
m.p. 208–2108C; H NMR (400 MHz, CDCl3) d 3.91 (s,
6H), 4.49–4.55 (m, 20H), 6.77 (s, 8H), 6.81–6.93 (m, 6H),
8.24 (s £ 4, 8H), 8.26 (s, 2H), 9.63 (s, 2H), 9.65
(s £ 2, 4H), 9.66 (s, 2H), 9.73 (s, 2H). Anal. calcd for
C58H60N10O22zH2O: C, 54.97; H, 4.93; N, 11.05. Found: C,
54.64; H, 4.77; N, 11.25.
(9) For related single-helical complexes, see: (a) Kawamoto, T.;
Hammes, B.S.; Haggerty, B.; Yap, G.P.A.; Rheingold, A.L.;
Borovik, A.S. J. Am. Chem. Soc. 1996, 118, 285–286. (b)
Zhang, F.; Bai, S.; Yap, G.P.A.; Tarwade, V.; Fox, J.M. J. Am.
Chem. Soc. 2005, 127, 10590–10599. (c) Dong, Z.;
Karpowicz, R.J., Jr; Bai, S.; Yap, G.P.A.; Fox, J.M. J. Am.
Chem. Soc. 2006, 128, 14242–14243. (d) Wiznycia, A.V.;
Desper, J.; Levy, C.J. Inorg. Chem. 2006, 45, 10034–10036.
(e) Dong, Z.; Yap, G.P.A.; Fox, J.M. J. Am. Chem. Soc. 2007,
129, 11850–11853.
(10) H2salamo¼1,2-bis(salicylideneaminooxy)ethane, see: (a)
Akine, S.; Taniguchi, T.; Nabeshima, T. Chem. Lett. 2001,
682–683. (b) Akine, S.; Taniguchi, T.; Dong, W.;
Masubuchi, S.; Nabeshima, T. J. Org. Chem. 2005, 70,
1704–1711.
Acknowledgement
This work was supported by Grants-in-Aid for Scientific Research
from the Ministry of Education, Culture, Sports, Science and
Technology, Japan.
References
(11) (a) Akine, S.; Taniguchi, T.; Nabeshima, T. Inorg. Chem.
2004, 43, 6142–6144. (b) Akine, S.; Nabeshima, T. Inorg.
Chem. 2005, 44, 1205–1207. (c) Akine, S.; Taniguchi, T.;
Nabeshima, T. Chem. Lett. 2006, 35, 604–605. (d) Akine, S.;
Dong, W.; Nabeshima, T. Inorg. Chem. 2006, 45, 4677–
4684. (e) Akine, S.; Akimoto, A.; Shiga, T.; Oshio, H.;
Nabeshima, T. Inorg. Chem. 2008, 47, 875–885. (f) Akine,
S.; Utsuno, F.; Taniguchi, T. Nabeshima, T. Eur. J. Inorg.
Chem. 2010, 3143–3152.
(1) (a) Lehn, J.-M. Supramolecular Chemistry, Concepts and
Perspectives; Wiley: Weinheim, 1995. (b) Piguet, C.;
Bernardinelli, G.; Hopfgartner, G. Chem. Rev. 1997, 97,
2005–2062.
(2) Huc, I. Eur. J. Org. Chem. 2004, 17–29.
(3) Hill, D.J.; Mio, M.J.; Prince, R.B.; Hughes, T.S.; Moore,
J.S. Chem. Rev. 2001, 101, 3893–4011.
(4) (a) Berl, V.; Huc, I.; Khoury, R.G.; Krische, M.J.; Lehn, J.-
M. Nature, 2000, 407, 720–723. (b) Dolain, C.; Maurizot,
V.; Huc, I. Angew. Chem., Int. Ed. 2003, 42, 2738–2740. (c)
Kolomiets, E.; Berl, V.; Odriozola, I.; Stadler, A.-M.;
(12) Dixon, D.W.; Weiss, R.H. J. Org. Chem. 1984, 49,
4487–4494.